Dicarbonyl compounds



Patented July 8, 1952 NITED cs PATENT OFFICE DICARBONYL COMPOUNDS Arthur H. Fischer, New York, N. Y., assignor to Minerecflorporation, New York, N. Y.

No Drawing. Application June 26, 1946, Serial No. 679,566 r (o1. zso iss) 4 Claims.

ample, as O-C2I-I4O and compounds such for example, as derivatives of ethylene glycol and diethylene glycol.

A dicarbonyl compound comprising a xanthate radical may be produced, for example, by reacting a salt or an acid comprising a xanthate radical with a dihaloformate to form a product having the following structural formula:

in which Y is a multivalent organic radical such, for example, as a glycol radical, and R. and R" are organic radicals such, for example, as ethyl radicals.

A dicarbonyl compound comprising a dithiophosphate radical may be produced, for example, by reacting a salt or an acid comprising an organic dithiophosphate radical with a dihaloformate to form a product having the following structural formula:

R!!! OBI/I! in which Y is a multivalent organic radical such,

for example, as a glycol radical, and R, R, R and R" are organic radicals such, for example, as ethyl radicals.

When substitution products of organic dithio acids containing organic radicals are employed, bis carbonyl dithio compounds containing corresponding organic radicals will be produced. Substitution products of acids and salts containing alkyl radicals or aryl radicals or both may be employed, and, in the above formulae, R, R", R' and R"" represent such radicals.

The use of di-substituted organic compounds comprising dithiophosphate radicals results in the production of tetra-substituted compounds. The use of (ii-substituted esters, for example, results in the production of tetra esters of his carbonyl dithiophosphate compounds.

The use of xanthates results in the production of his carbonyl xanthate compounds containing the organic radicals or groups present in the reagents employed.

In producing compounds in accordance with the invention, substitution products of acids and salts containing alkyl radicals or aryl radicals or both may be employed.

The compounds of the invention are suitable for various uses, and they may be employed with particular advantage as mineral collecting agents in the concentration of minerals by froth flotation.

Among the compounds found most suitablefor' use in flotation concentration processes are:

Compound A A reaction product of sodium ethyl xanthate and ethylene glycol chloroformate having the following structural formula:

-SCO-UzH4OC-S I g II II g 0 r 0 Ethylene glycol bis carbonyl ethyl xanthate Compound B A reaction product of sodium ethyl xanthate and diethylene glycol chloroformate having the following structural formula:

O 2H4OC2H-l-OCS--C g ll II ll 0 o s Diethylene glycol bis carbonyl ethyl xanthate Compound C A reaction product of sodium diethyl dithiophosphate and diethylene glycol chloroformate having the following structural formula:

C H O O CzH5 0 131 0 1 S-C-OC H4OO H OO-S-P l t O l Diethylene glycol bis carbonyl diethyl dithiophosphate Compound D i A reaction product of sodium butyl xanthate and diethylene glycol chloroformate having the following structural formula;

Diethylene glycol bis carbonyl butyl xanthate The use of the compounds of the invention for the concentration of minerals is described and claimed in my copending application Serial No. 679,565, filed June 26, 1946, now Patent No. 2,501,269, issued March 21, 1950.

The following examples illustrate methods of preparing compounds in accordance with my inventionysuitable'for use in the. flotation methods or processes'of my invention:

Example I Preparation of the reaction product of sodium ethyl xanthate and diethylene glycol'chloroformate.

300 grams of pure sodium ethyl xanthate-2H2O (13% in excess of theory) were dissolved inlliter of water in a 2 liter flask provided with stirrer .and thermometer. 170.4 grams of diethylene glycol .chloroformate were .added to this solution .over a period of. flfteenminutes. The temperature of the reaction mixture rose slowly to'30 C. .Ifhe mixture was heated .to 45 C. The heating .was then discontinuedand the temperature slowly iell to that ofv the room. The ,totaltime of reaction was five hours.

Ihe oily product was separated and the aqueous layer-extracted with carbonrbisulfide.

The oilyproductand the carbon bisulfide ex- -tracts 'werecombinedand the carbon bisulfide was distilled ofi en vacuo.

.Theproduct was a-yellow oil. The yield was 241 grams which is 31.17% of the theoretical amount for the above equation.

Analysis: Sulfur calculated, 31.86%; sulfur found. 31.4

Preparation of the reaction product of sodium diethyl dithiophosphate and ethylene glycol chroformate.

4 I claim: 1. A compound having the structural formula:

"OR' or." -s -c--Y--c--s--o till and in which R .andR" represent the sameradi- .calselectedfrom the group consisting of ethyl and butyl.

.2. A compound having the structural formula:

in which R and R". represent an ethyl radical.

3. A compound having the structural formula:

OR OR --S-C-O-C2H4---O -Cflfh-O-C'--S( J II II I! H s 0 in which R and R"' represent an ethyl radical.

153.1 grams of 2.95% ..die,thyl dithiophosphoric ..,acid were dissolved in 500 ml..of dry acetone and .converted to the sodium .salt by neutralization with 44".! grams of anhydrous sodium carbonate (108% of theory) which was added slowly. This mixture, contained in a 1 liter flask provided with a stirrer and thermometer, was stirred for fifteen minutes after the addition of the sodium carbonate, to complete the neutralization. '73 grams of ethylene glycol chloroformate'were then added in 20 minutes, the temperature was kept below 25 C. hymeans of a cooling bath, and the stirring was .continuedfor two 'hoursafterthe ethylene glycol chloroformate had beenadded.

The reaction mixture was'diluted with water and the .water insoluble oily reaction product was separated and .dried by warming to C. en vacuo.

191 grams of product were obtained which is a theoretical yield.

Analysis: Sulfur :calculated, 26.36%; sulfur found, 26.35%.

.Dicarbonyl compounds containing other organic radicals maybeproduced by the same ,procedure or by similar procedures when employing organic reagents containing such other organic radicals.

4. A compound having the structural formula:

OR OR A|f-s-fi-O-C2H4OCJH4O%-S H s o o s .in WhichJRandLR represent a butyl radical.

ARTHUR H. FISCHER.

REFERENCES CITED The following .references .are .of record in .the file of .this patent:

UNITED STATES PATENTS OTHER REFERENCES Chem. Abstracts, vol. 7, page .2187 (1913), abstracting. article by-Biilman .et al. 

1. A COMPOUND HAVING THE STRUCTURAL FORMULA 